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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa
a r t i c l e i n f o a b s t r a c t
Article history: Woodplastic composites (WPCs) undergo cyclic dimensional changes due to periodic absorption and
Received 29 December 2007 desorption of moisture, and the resulting loss of mechanical integrity can be ameliorated using a coupling
Received in revised form 13 July 2008 agent. Another solution is better processing. Here, we examine injection-molded, polypropylene (PP)-
Accepted 14 July 2008
based woodplastic composites and investigate why the rate of moisture absorption can be reduced
by changing extruder operating conditions. At a given wood content, the mechanical properties were
found to be similar, but the use of high screw rotation speeds, whether in the co-rotation or counter-rota-
Keywords:
tion modes, and long residence times gave lower rates of moisture absorption even in the absence of a
A. Woodplastic composites (WPCs)
B. Environmental degradation
coupling agent.
D. Electron microscopy 2008 Elsevier Ltd. All rights reserved.
E. Extrusion
1359-835X/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2008.07.013
S.-K. Yeh, R.K. Gupta / Composites: Part A 39 (2008) 16941699 1695
absorption is closely related to the quality of wood our, batch-to- according to ASTM D638, while the impact test refers to ASTM
batch differences between different bags of wood our may affect D256. The cross-sectional area of the tensile samples was
experimental results. To prevent this from happening, two 22.7 kg 13 mm 3.2 mm while the overall length of the samples was
bags of maple wood our having the same lot number were pre- 165 mm (ASTM D638, Type I). Because WPCs generally showed rel-
mixed in a box for these experiments to ensure consistency of re- atively low impact strength in the standard Izod impact test, the
sults. The PP-g-MA coupling agent used, PB3200, was from reversed notch impact test method was applied.
Chemtura; it had a molecular weight of 120,000 (g/mol) with The rate of water absorption of the WPCs was determined using
1.0 wt% maleic anhydride content. An antioxidant, Naugard B-25, a blot and weigh method. Three weighed samples were taken
was also used at the 0.1 wt% level to prevent polymer degradation from each batch to conduct this test. The typical injection-molded
during melt compounding. It is a blend of phenol and phosphite, impact test sample of 12.5 mm 64 mm 3.175 mm was put on a
and it was also provided by Chemtura. Note that PP-g-MA pellets tray of desiccants and dried in a vacuum oven at 80 C for 12 h.
were hand mixed with polypropylene pellets in a bag before being After that, each sample was immersed in a sealed container full
fed to the extruder. Also, the wood our was pre-dried in an oven of distilled water at room temperature and was periodically re-
at 100 C for 7 h to ensure that the moisture content was below moved and weighed. The results of the water absorption test were
1 wt%. plotted as percentage weight gained versus time of immersion.
WPC samples were compounded using a Leistritz Micro-27 These samples are considered to have reached the equilibrium
twin-screw extruder; half the samples were processed with co- moisture when the weight gain was less than 3 mg within a 2-
rotation screws, and the other half were processed with counter- week period.
rotation screws. The experimental matrix is listed in Table 1, while To determine if processing conditions altered the size distribu-
the designs of the co-rotation and counter-rotation screws are tion of the wood particulates in the WPCs, the impact samples
show in Figs. 1 and 2, respectively. The materials were fed into from each batch of WPCs were treated with hot xylene to remove
the extruder with K-Tron loss-in-weight powder and pellet feed- the polymer matrix. After the matrix was dissolved, the magnetic
ers. The total feeding rate was controlled at 2.4 kg/h, and all the stirrer was stopped, while the hot plate was kept on for a further
samples contained 50 wt% wood our. The barrel temperature 40 min. During this time, the wood our settled to the bottom of
was controlled at 165180 C from hopper to the die, while the the ask, and the supernatant was drained. The precipitate was
screw rotation speed was xed at either 85 or 150 rpm. As men- then diluted with fresh xylene to prevent any remaining polypro-
tioned in Table 1, some of the WPC samples that were compounded pylene from coming out of solution during ltration. The mixture
at 85 rpm were passed through the extruder twice to investigate was boiled again and hot ltered to separate wood our from the
the effect of doubling the residence time on the properties of solution. The extracted wood our was nally oven dried at 70 C
WPCs. WPC strands emerging from the die were cooled in a water for 48 h. The extracted wood our from each batch was dusted
bath and then pelletized for further processing. These details on carbon tapes and then observed using a Hitachi S-4700 FESEM
should allow for easy duplication of the results reported here. to obtain the morphology of wood our. In addition, the particle
The compounded WPC pellets were dried at 85 C for 6 h and size distribution of wood our was analyzed with a Shimadzu
then injection molded using a Battenfeld injection molding ma- SALD-3101 particle analyzer. For this instrument, the refractive in-
chine to produce standard ASTM samples. The tensile and stiffness dex was set at 1.7 and isobutyl alcohol was used as a dispersing
properties and also the impact strengths of these samples were agent to prevent particle aggregation. Before making measure-
measured using an Instron 5869 universal testing machine and a ments, the solution was mixed with a circulation pump and soni-
BLI impact tester, respectively. The tensile strength was analyzed cated with an ultrasonicator for 1 min. The tests were repeated
three times to ensure that ultrasonication did not affect the parti-
cle size distribution.
Table 1 The optical properties of the WPCs were measured using a
Composition of various polypropylene/wood our composites Macbeth Color-eye 7000 color meter. These tests were conducted
courtesy of GE Plastics (now SABIC Innovative Plastics) in Wash-
Run Screw rotation speed Pass Wood AO PP-g-MA (wt%) in
(rpm) (wt%) (wt%) wood ington, WV. The results are presented in CIELab color space (L*,
a*, b*). Here, L* means lightness and L* ranges from 0 (black) to
1 85 1 50 0.1 0
2 85 1 50 0.1 2
100 (white). An impact sample was chosen from each batch of
3 85 1 50 0.1 4 samples, and the color was measured at three different locations.
4 85 2 50 0.1 0 The average value of lightness is reported here.
5 85 2 50 0.1 2 Finally, the IR spectrum of wood our was obtained using a
6 85 2 50 0.1 4
PerkinElmer Spectrum One FT-IR and employing oven-dried IR-
7 150 1 50 0.1 0
8 150 1 50 0.1 2 grade potassium bromide as diluent. Around 1 mg of wood our
9 150 1 50 0.1 4 was mixed with KBr powder using a mortar and pestle and then
compressed into a disk. Typically, the samples were scanned about
Samples were made with both co-rotation and counter-rotation screws. 18 batches
of samples were compounded. 100 times with a resolution of 4 cm 1.
12% 0% CA 85rpm E2
To understand if changing processing conditions lead to
10% 0% CA 150rpm changes in the structure of WPCs, the results of measuring the
8% average particle size using the Shimadzu SALD-3101 particle size
2% CA 85rpm
6%
analyzer are shown in Figs. 5a(a) and 5b(b). A clear trend can be
2% CA 85rpm E2 seen from Fig. 5a(a) which displays data for co-rotating screws: a
4%
2% CA 150rpm high screw speed (150 rpm) and a long residence time (85 rpm, 2
2% passes) reduced the size of wood our, with the particle size of
4% CA 85rpm
0% wood our processed with the longer residence time being ner
0 40 80 120 160 200 240 280 320 4% CA 85rpm E2 than for the one processed with the higher screw speed.
Time [days] Since the laser particle analyzer assumes that each particle is a
Fig. 3. Moisture content as a function of time for WPCs made with co-rotation sphere, and since wood particulates are actually cylindrical, an
screws. optical microscope was used to conrm the results from the laser
S.-K. Yeh, R.K. Gupta / Composites: Part A 39 (2008) 16941699 1697
Table 3
Rate of water absorption and equilibrium moisture of WPCs
PP-g-MA to Co-rotation Pass Rate of water Equilibrium moisture Counter Pass Rate of water Equilibrium moisture
wood (wt%) (rpm) absorption (wt%/day) content (wt%) rotation (rpm) absorption (wt%/day) content (wt%)
0 85 1 0.234 (0.001) 12.81 (0.01) 85 1 0.249 (0.003) 12.36 (0.02)
0 85 2 0.203 (0.002) 12.57 (0.06) 85 2 0.199 (0.001) 12.06 (0.02)
0 150 1 0.141 (0.0005) 11.25 (0.03) 150 1 0.22 (0.001) 11.65 (0.02)
2 85 1 0.099 (0.001) 12.02 (0.03) 85 1 0.113 (0.002) 11.74 (0.02)
2 85 2 0.090 (0.001) 11.87 (0.02) 85 2 0.085 (0.0004) 11.11 (0.03)
2 150 1 0.068 (0.001) 10.76 (0.01) 150 1 0.091 (0.001) 10.76 (0.02)
4 85 1 0.081 (0.001) 12.06 (0.03) 85 1 0.078 (0.001) 11.59 (0.02)
4 85 2 0.068 (0.0003) 11.84 (0.0002) 85 2 0.068 (0.0004) 11.19 (0.02)
4 150 1 N/A N/A 150 1 0.072 (0.001) 10.72 (0.06)
a 200
160
Particle Size (um)
40
0
0 2 4
PP-g-MA to Wood (w t%)
b 200
160
Particle Size (um)
40
0
0 2 4
PP-g-MA to Wood (wt%)
Fig. 5. (a) Particle size of wood our extracted from WPCs processed with co-
rotation screws. (b) Particle size of wood our extracted from WPCs processed with
counter-rotation screws.
a 45
42
85 rpm 1pass
L*
85rpm 2 pass
150rpm 1pass
39
36
0 2 4
PP-g-MA to Wood (w t%)
b 45
42
85 rpm 1pass
L*
85rpm 2 pass
150rpm 1pass
39
36
0 2 4
PP-g-MA to Wood (w t%)
Fig. 7. (a) Lightness of WPCs processed with co-rotation screws. (b) Lightness of
WPCs processed with counter-rotation screws. Fig. 8. Wood our extracted from samples (a) with PP-g-MA, and (b) without PP-g-
MA. Samples were processed with counter-rotation screws at 150 rpm.
the co-rotation screws provide more severe agitation as compared by FT-IR [21]. We also observed the wood our by a scanning elec-
to the counter-rotating screws. This is not intended to be a general tron microscope. Wood our extracted from WPCs was lightly
statement, and it is true only for the screw designs shown in Figs. 1 dusted on a carbon tape using a needle. Typical SEM pictures of
and 2. Separately, other researchers have reported that ner wood wood our taken from WPCs made with and without PP-g-MA
our particulates tend to reduce the water absorption rate of WPCs are shown in Fig. 8(a) and (b), respectively. As can be seen from
[5]. Thus, while the results in this study are consistent with those Fig. 8(a), there are only a few aggregates in the wood our treated
available in the literature, they do not explain why ner particu- with PP-g-MA. On the other hand, wood our tends to form aggre-
lates result in a reduction in the rate of moisture absorption. gates in the absence of PP-g-MA which can be seen clearly in Fig.
The results of color measurement shown in Figs. 7a(a) and 7b(b) 8(b); this is possibly because the hydroxyl groups on the surface
indicate that samples processed with co-rotating screws are darker of wood our form hydrogen bonds and attract each other [2].
than those processed with counter-rotating screws under the same Therefore, adding PP-g-MA denitely changes the chemical nature
process conditions. This is because higher L* values mean greater of the surface of wood our.
lightness. This again indicates that the co-rotation screws used in
this work are more severe than the counter-rotating screws. Also, Table 4
passing WPCs through the extruder twice made WPCs darker than Density of WPCs made with different compounding processes
when processed with a higher screw speed. Overall, though, the PP-g-MA to Co- Pass Density (g/ Counter Pass Density (g/
differences in lightness are small, and the appearance of all the wood rotation cm3) rotation cm3)
sample batches was acceptable. (wt%) (rpm) (rpm)
Since the addition of PP-g-MA decreases the rate of water 0 85 1 1.089 (0.002) 85 1 1.083 (0.001)
absorption signicantly, it is of interest to examine the infra-red 0 85 2 1.084 (0.002) 85 2 1.086 (0.001)
spectrum of wood our with and without PP-g-MA after com- 0 150 1 1.064 (0.002) 150 1 1.082 (0.001)
2 85 1 1.09 (0.001) 85 1 1.086 (0.001)
pounding. Before carrying out the measurements, wood our ex-
2 85 2 1.09 (0.002) 85 2 1.088 (0.001)
tracted from WPCs was pre-dried in an oven at 80 C to ensure 2 150 1 1.065 (0.001) 150 1 1.08 (0.001)
that the moisture content was less than 1 wt%. Unfortunately, no 4 85 1 1.088 (0.003) 85 1 1.086 (0.002)
difference could be seen between the two IR spectra because wood 4 85 2 1.089 (0.002) 85 2 1.088 (0.001)
4 150 1 1.086 (0.002) 150 1 1.086 (0.002)
our itself contains ester groups. Thus, the esterication reaction
between hydroxyl groups and maleic anhydride cannot be seen The numbers in parenthesis are standard deviation values.
S.-K. Yeh, R.K. Gupta / Composites: Part A 39 (2008) 16941699 1699
Table 5
ANOVA table of WPCs processed with different processing methods and different PP-g-MA loading level
df SS MS F Critical F
A: Screw geometry 1 3.715E 07 3.715E 07 MSa/MSe 1948.092 4.2597
B: Processing methods 2 1.179E 06 5.893E 07 MSb/MSe 3090.053 3.4029
C: PP-g-MA content 1 1.224E 05 1.224E 05 MSc/MSe 64171.613 4.2597
AB 2 4.676E 07 2.338E 07 MSab/MSe 1225.963 3.4028
AC 1 8.614E 08 8.614E 08 MSac/MSe 451.729 4.2597
BC 2 1.862E 07 9.309E 08 MSbc/MSe 488.137 3.4028
ABC 2 1.502E 07 7.511E 08 MSabc/MSe 393.856 3.4028
Error 24 4.577E 09 1.907E 10
The density of WPCs was measured to see if the wood our had the West Virginia EPSCoR Challenge Grant Program and partly by
been changed in any way during compounding. The density was contract number DE-FC26-00FT40598 from the U.S. Department
determined simply by dividing the weight of a WPC sample by of Energy. During the last year of his stay, Shu-Kai Yeh received
its volume. Results are shown in Table 4. It is found that the den- an assistantship from funds available to Professor Gupta through
sity of most WPCs is around 1.081.09 g/cm3 except in the case the George and Carolyn Berry Chair.
of samples made with the co-rotating screws at the higher screw
speed of 150 rpm. Recall that these samples are the ones which References
exhibited a much lower rate of water absorption and equilibrium
moisture content. It is speculated that the co-rotating screws, [1] http://www.epa.gov/oppad001/reregistration/cca/.
[2] Bledzki AK, Gassan J. Composites reinforced with cellulose based bers. Prog
being the more severe ones, caused a larger increase in tempera- Polym Sci 1999;24:22174.
ture inside the extruder during compounding, and this resulted [3] Stark N. Inuence of moisture absorption on mechanical properties of wood
in a loss of some hydrophilic volatile organic compounds from our-polypropylene composites. J Thermoplast Compos 2001;4(5):42132.
[4] Marcovich NE, Reboredo MM, Aranguren MI. Moisture diffusion in polyester
the wood our [22]. This might explain the lowered density and woodour composites. Polymer 1999;40(26):731320.
also the decreased rate of water absorption of WPCs processed [5] Steckel V, Clemons CM, Thoemen H. Effects of material parameters on the
with co-rotating screws. It might be argued that the extreme pro- diffusion and sorption properties of wood-our/polypropylene composites. J
Appl Polym Sci 2006;103(2):75263.
cessing conditions result in ner particles that reduce moisture [6] Zhang YL, Zhang SY, Chui YH. Water vapor adsorption and volumetric swelling
content, but this would be accompanied by an increase in density. of melt-impregnated woodpolymer composites. J. Appl Polym Sci
Obviously, additional studies need to be done to determine the 2006;102(3):266876.
[7] Bledzki AK, Sperber VE, Specht K, Letman MA. Effect of dened waxes and
true explanation for the observations reported here.
coupling agents on moisture behavior of injection molded woodber-
Since the experiments were planned as a three-factor factorial reinforced PP composites. In: Proceedings of 8th international conference on
design with xed effect, the data could be analyzed by statistics woodberplastic composites, Madison, WI, May 2005.
[8] Stark NM. Effect of weathering cycle and manufacturing method on
to ensure that the results are statistically signicant. Here, only
performance of wood our and high-density polyethylene composites. J Appl
the samples containing 0 and 2 wt% of PP-g-MA are included in Polym Sci 2006;100(4):313140.
the analysis to avoid interference from samples processed with [9] Pilarski JM, Matuana LM. Durability of wood ourplastic composites exposed
co-rotation screws, 150 rpm and 4 wt% PP-g-MA. The analysis of to accelerated freezethaw cycling II. High density polyethylene matrix. J
Appl Polym Sci 2006;100(1):359.
variance (ANOVA) is listed in Table 5. All of the F values listed in [10] Schirp A, Wolcott MP. Inuence of fungal decay and moisture absorption on
this table are much larger than the critical F value. Thus, although mechanical properties of extruded woodplastic composites. Wood Fiber Sci
the coupling agent amount is the most important of the three vari- 2005;37(4):64352.
[11] Wang W, Sain M, Cooper PA. Hygrothermal weathering of rice hull/HDPE
ables, every variable including screw geometry and the processing composites under extreme climatic conditions. Polym Degrad Stabil
method is statistically signicant. 2005;90(3):5405.
[12] Wang WH, Morrell JJ. Effects of moisture and temperature cycling on material
properties of a wood/plastic composite. Forest Prod J 2005;55(10):813.
4. Conclusions [13] Stark NM, Matuana LM. Surface chemistry and mechanical property changes of
wood-our/high-density-polyethylene composites after accelerated
weathering. J Appl Polym Sci 2004;94(6):226373.
While a change of extrusion processing variables does not sig- [14] Stark NM, Matuana LM, Clemons CM. Effect of processing method on surface
nicantly affect the tensile strength and modulus of WPCs, it does and weathering characteristics of wood-our/HDPE composites. J Appl Polym
Sci 2004;93(3):102130.
affect the moisture absorption behavior. A long residence time and
[15] Bledzki AK, Letman M, Viksne A, Rence L. A comparison of compounding
higher screw speeds not only result in smaller particulate sizes in processes and wood type for wood brePP composites. Composites A
the compounded WPCs, they also lower the rate of water absorp- 2005;36:78997.
tion. The reduction in moisture absorption rate ranges from 10% [16] Yeh SK, Al-Mulla A, Gupta RK. Effect of the coupling agent on the
properties of PNC-based wood/plastic composites. J Polym Eng 2006;26(8
to 40%, and this happens without a change in the mechanical prop- 9):783804.
erties of the WPCs. It is found that the density of the WPCs is de- [17] Wang Y, Chan HC, Lai SM, Shen HF. Twin screw compounding of PE-HD wood
creased under severe compounding conditions, and this offers a our composites. Int Polym Proc 2001;XVI(2):1007.
[18] Rowland SP, Roberts EJ. Natural of accessible surfaces in the microstructure of
clue to the reason for the observed reduction in the rate of water cotton cellulose. J Polym Sci Pol Chem Ed 1972;10(8):224761.
absorption. It is speculated that moisture absorption rate decreases [19] Gozdz AS, Weigmann HD. Surface characterization of intact bers by inverse
when severe compounding conditions are employed because these gas chromatography. J Appl Polym Sci 1984;29(12 pt 1):396579.
[20] Hon DNS. Chemical modication of lignocellulosic materials. In: Kiguchi M,
cause the loss of hydrophilic volatile organic compounds contained editor. Surface modication and activation of wood. New York: Marcel Dekker;
in the WPCs. 1996 [chapter 8].
[21] Qiu WL, Endo T, Hirotsu T. Interfacial interactions of a novel mechanochemical
composite of cellulose with maleated polypropylene. J Appl Polym Sci
Acknowledgements
2004;94(3):132635.
[22] Rizvi GM, Park CB, Lin WS, Guo G, Pop-Iliev R. Expansion mechanisms of
The wood our and PP-g-MA were provided by American Wood plastic/wood-ber composite foams with moisture, dissolved gaseous
volatiles, and un-dissolved gas bubbles. Polym Eng Sci 2003;43(7):134760.
Fibers, and Chemtura, respectively. This work was funded partly by